Laser-excited phosphorescence spectrum of C3S2 in an Ar matrix

The phosphorescence spectrum of C₃S₂ was observed in a low-temperature Ar matrix with excitation of an Ar⁺ laser. The spectrum consists of a very strong 0-0 band at 18 287 cm^?1 and well-resolved progressions in the ν₂, ν₅, ν₆, and ν₇ vibrations. Side bands were found on the high-energy sides of some transitions. The separation between the main and side bands is 23 cm^?1. Polarization analysis suggests that C₃S₂ is linear symmetric in the Phosphorescent state as in the ground electronic state. On the basis of symmetry considerations and a qualitative evaluation of spin-orbit coupling, the phosphorescent state is assigned to ³Σ_u^? with Σ_u⁺ and Π_u components split by spin-spin interaction. The Σ_u⁺ level is lower than the Π_u one by 23 cm^?1 and the main and side band emissions start from the Σ_u⁺ and Π_u levels, respectively. The Σ_u⁺ component seems to acquire allowed character from a ¹Σ_u⁺ state by spin-orbit coupling and from bent ${}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}\text{(}{}^1\text{B}{}_2\text{)}$ and ${}^1\text{Δ}{}_{\mathrm{g}}\text{(}{}^1\text{A}{}_1\text{+}{}^1\text{B}{}_2\text{)}$ states by ν₅ vibronic coupling. Mixing of the Σ_u⁺ and Π_u components through ν₅ is responsible for most of the side bands. The ν₅ frequency is estimated to be 160 ± 20 cm^?1 in the ³Σ_u^? state from the intensities of ν₅ progression bands and from the ground-state frequency, 411 cm^?1.     

3Σu−-3Σu+ coupling in the O2B3Σu− predissociation

The role of $\text{B}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{-2}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ spin-orbit mixing in the O₂ Schumann-Runge predissociation is investigated. The $\text{2}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state is found to cross the $\text{B}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}$ state near 2.0 Å with an interaction matrix element of approximately 55 cm^?1. This state contributes to the widths of the Bv ≥ 6 levels, but introduces only small level shift perturbations. When the partial widths due to the ${}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{-}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ interaction are added to the previously calculated widths due to the ⁵Π_u, ³Π_u, and ¹Π_u states, reasonable agreement is obtained with experimental measurements on O¹⁶O¹⁶ and O¹⁸O¹⁸. The possibility of non-Lorentzian line profiles and the dependence of the width on rotational quantum number is investigated. The approximation of the spin-orbit matrix element by its value at the crossing point is shown to be a good approximation for calculating the second difference perturbations.     

Energy levels of low lying triplet states of N2 from infrared emission studies

A theoretical model used to describe the $\text{B′}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}$ and B³Π_g states of N₂ is presented. Using recently acquired high resolution spectra of the $\text{B′}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{→ B}{}^3\text{Π}{}_{\mathrm{g}}$ (0-0) band, rotational energy levels of the v = 0 vibrational levels of these two states are generated with this model. These levels are in excellent agreement with those obtained using a combination differences technique. The precision of the model generated levels is 0.01 cm^?1. The previously unpublished rotational levels of Dieke and Heath for the $\text{A}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$, B³Π_g and C³Π_u states are referenced to the $\text{N}{}_2\text{X}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ (v = 0, J = 0) ground level and tabulated here. Estimates of the precision of their work are made.     

The infrared part of the C2 Phillips system (2.3–0.9 μm)

Line positions and molecular constants for the 0-0, 1-0, 2-0, 0-1, 2-1, 3-1, 0-2, 1-2, and 4-2 bands of the C₂ Phillips system ($\text{A}{}^1\text{Π}{}_{\mathrm{u}}\text{-X}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$) are reported. Among them, five bands have not been reported previously. Rotational perturbations have been observed in the previously unobserved v = 1 level of the $\text{A}{}^1\text{Π}{}_{\mathrm{u}}$ state. This state is perturbed by the $\text{c}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state which was discovered by Ballik and Ramsay. These observations provide new information regarding the perturbing state. In particular, the minimum of the potential energy for the $\text{c}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state has been found to be at 9227.4 cm^?1 instead of 13 310 cm^?1, which was the previous T_e value for this electronic state.     

Spectrum and structure of the He2 molecule: Characterization of the singlet and triplet states associated with the UAO's 4s, 4dσ, 4dπ, and 4dδ

The emission spectrum of the He₂ molecule has been rephotographed in the ～4000–～5700 Å region and the $\text{4d(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}\text{) → 2pπ}{}^3\text{Π}{}_{\mathrm{g}}$, $\text{4d(}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^1\text{Π}{}_{\mathrm{u}}\text{,}{}^1\text{Δ}{}_{\mathrm{u}}\text{) → 2pπ}{}^1\text{Π}{}_{\mathrm{g}}$, $\text{4s}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 2pπ}{}^3\text{Π}{}_{\mathrm{g}}$ and $\text{4s}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 2pπ}{}^1\text{Π}{}_{\mathrm{g}}$ transitions analyzed. The 4dδj³Δ_u, 4dπj³Π_u, $\text{4dσj}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ and $\text{4sh}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ states have been characterized through v = 2 and the 4dδJ¹Δ_u, 4dπJ¹Π_u, $\text{4dσJ}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$, and $\text{4sH}{}^1\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ states for v = 0. The term levels for these perturbed and l-uncoupled states have been confirmed (a) by analyses of bands with common levels from Δv = 0, ±1 sequences and (b) by analyses of the transitions between the above states from 4d and 4s and the $\text{c}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ and $\text{C}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ states associated with 3pσ. Molecular constants are reported which have been partially corrected for the effects of l-uncoupling and the homogeneous perturbations between the state pairs J, H and j, h.     

Lifetime of electronic states of CO2+

The radiative lifetimes of the $\text{A}\text{?}{}^2\text{Π}{}_{\mathrm{u}}$ and $\text{B}\text{?}{}^2\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ states of CO₂⁺ were measured by means of the delayed coincidence method. Excitation was performed by a pulsed electron beam incident on CO₂. The results of these measurements are 115 ± 5 nsec for the $\text{A}\text{?}{}^2\text{Π}{}_{\mathrm{u}}$ state and 126 ± 3 nsec for the $\text{B}\text{?}{}^2\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ state.     

Predissociation and Λ-doubling in the even-parity Rydberg states of the nitrogen molecule

Predissociations in the y¹Π_g and $\text{x}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}$ Rydberg states of N₂ (configurations $\text{1π}{}_{\mathrm{u}}{}^{\mathrm{?1}}\text{4pσ}$ and $\text{1π}{}_{\mathrm{u}}{}^{\mathrm{?1}}\text{3pπ}$, respectively) and their likely causes, are discussed. Peaking of rotational intensity at unusually low J values, without sharp breaking off, is interpreted as due to case c^? or case cⁱ predissociation. Λ doubling in the y state, attributed to interactions with the $\text{x}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}$ state and with another, ¹Σ⁺, state of the same electron configuration as x, is analyzed. From this analysis the location of the (unobserved) ${}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ state, here labeled x′, is obtained. It is concluded that the predissociation in the Π⁺ levels of the y state is an indirect one mediated by the interaction with x′ coupled with predissociation of x′ by a ${}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{?}}$ state dissociating to ${}^4\text{S +}{}^2\text{P}$ atoms: combined, however, with perturbation of the y state by the k¹Π_g Rydberg state (configuration $\text{3σ}{}_{\mathrm{g}}{}^{\mathrm{?1}}\text{4dπ}$), whose Π⁺ levels are completely predissociated.     

The 280-nm absorption system of benzoyl fluoride

Benzoyl fluoride exhibits a weak, discrete absorption system in the region 290 – 260 nm. Vibrational structure associated with the C₆H₅COF and C₆D₅COF isotopes has been analyzed in detail. The C₆H₅COF and C₆D₅COF origin bands lie at 35 685 and 35 829 cm^?1, respectively. The intensity in the spectrum is principally associated with two progressions, ν′₁₉, the breathing vibration of the benzene ring and ν′₂₄, a COF in-plane bend, and sequence bands involving the COF torsion motion ν₃₆. The $\text{C}{}_6\text{H}{}_5\text{COF}\text{C}{}_6\text{D}{}_5\text{COF}$ν₁₉, ν₂₄, and ν₃₆ vibrational frequencies are respectively 1005/-, $\text{376}\text{357}\text{,}\text{and}\text{57}\text{55}\text{cm}{}^{\mathrm{?1}}$ in the ground state and $\text{950}\text{919}\text{,}\text{348}\text{331}\text{,}\text{and}\text{89}\text{85}\text{cm}{}^{\mathrm{?1}}$ in the excited state. The barriers to rotation of the COF group are estimated from the torsional frequency data to be 1450 and 3450 cm^?1 in the ground and excited electronic states, respectively.     

The spectrum and structure of the He2 molecule: Characterization of the triplet states associated with the UAO's 4pσ, 5pσ, and 6pσ

The emission spectrum of the He₂ molecule has been rephotographed in the ～3200–4100 Å region and the $\text{4pσ g}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{→ 2s a}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$, $\text{5pσ k′}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{→ 2s a}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$, and $\text{6pσ n}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{→ 2s a}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ transitions analyzed. The g, k′, and n states, which have not been reported previously, are characterized through v = 1, 2, and 1, respectively. Several small accidental perturbations have been observed in the rotational manifolds of the k′ and n states.     

Vibrational spectra and force constants of symmetric tops: High resolution spectra of monoisotopic H3SiCl in the 2200-cm−1 region and rovibrational analysis of the ν1 and ν4 fundamentals

The gas phase infrared spectra of monoisotopic H₃Si³⁵Cl and H₃Si³⁷Cl have been studied in the $\text{ν}{}_1\text{ν}{}_4$ region near 2200 cm^?1 with a resolution of 0.012 and 0.04 cm^?1, respectively, and rotational fine structure for ΔJ = ±1 branches has been resolved. In addition, some information on ν₃ + ν₄ of H₃Si³⁵Cl near 2750 cm^?1 has been obtained. ν₁ and ν₄ are weakly coupled by Coriolis x, y resonance, $\text{B}\text{Ω}{}_{14}\text{ζ}{}_{14}\text{～ 2 × 10}{}^{\mathrm{?3}}\text{cm}{}^{\mathrm{?1}}$, only the upper states K′ = 2, l = 0 and K′ = 1, l = ?1 being substantially affected. Local perturbation due to rotational l(±1, ±1)-type resonance with ν₃ + ν₅⁺¹ + ν₆⁺¹ and ν₃ + ν₅⁺¹ + ν₆^?1 is revealed in the ΔK = +1 and ?1 branches, respectively. From a fit of the experimental line positions, standard deviations of 1.4 and 3.8 × 10^?3 cm^?1, respectively, to a model with five interacting levels conventional excited state parameters and interaction constants have been obtained. In $\text{H}{}_3\text{Si}{}^{35}\text{Cl}\text{H}{}_3\text{Si}{}^{37}\text{Cl}$ the fundamentals are ν₁, $\text{2201.94380(15)}\text{2201.9345(7)}$ and ν₄, $\text{2209.63862(8)}\text{2209.6254(2)}\text{cm}{}^{\mathrm{?1}}$, respectively. Q branches of the “hot” band (ν₃ + ν₄) ? ν₃ and of ν₄ of the ²⁹Si and ³⁰Si species have been detected.     

Coriolis intensity perturbations in the SO2 molecule: Experimental determination of the relative signs of (∂μ∂Qi)

The Coriolis interactions between ν₁ and ν₃, and between ν₂ and ν₃ in SO₂ have been analyzed to obtain the signs of the products $\text{ζ}{}_{3.1}{}^{\mathrm{c}}\text{(}\text{?μ}{}^{\mathrm{a}}\text{?Q}{}_3\text{)(}\text{?μ}{}^{\mathrm{b}}\text{?Q}{}_1\text{)}$ and $\text{ζ}{}_{3.2}{}^{\mathrm{c}}\text{(}\text{?μ}{}^{\mathrm{a}}\text{?Q}{}_3\text{)(}\text{?μ}{}^{\mathrm{b}}\text{?Q}{}_2\text{)}$. It has been found that both of the signs of these products are positive. Then, relative signs of ($\text{?μ}\text{?Q}{}_1$) have been determined using the calculated values of the Coriolis zeta constants for the present definition of the normal coordinates. The obtained sign combination of ($\text{?μ}\text{?Q}{}_{\mathrm{i}}$) is ±(+?+), which agrees with the one predicted by the molecular orbital calculations. Using the sign combination (+?+), the polar tensors of S and O atoms were also calculated.     

Spectrum and structure of the He2 molecule: Characterization of the triplet states associated with (1σg)2(1σu)nsσ, ndσ, ndπ, and ndδ (n = 5–12)

Emission spectra for the electronic transitions $\text{ndλ(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}\text{) → 2pπ b}{}^3\text{Π}{}_{\mathrm{g}}\text{(n = 5–12)}$, $\text{nsσ}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 2pπ b}{}^3\text{Π}{}_{\mathrm{g}}\text{(n = 5–12)}$, $\text{ndλ(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}\text{) → 3pσ c}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{(n = 5–10)}$, $\text{nsσ}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 3pσ c}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{(n = 5–11)}$, $\text{ndλ(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}\text{) → 3pπ e}{}^3\text{Π}{}_{\mathrm{g}}\text{(n = 6–11)}$, $\text{nsσ}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 3pπ e}{}^3\text{Π}{}_{\mathrm{g}}\text{(n = 6–11)}$, $\text{nsσ}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{→ 4pσ g}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{(n = 9–11)}$, and $\text{10dδ}{}^3\text{Δ}{}_{\mathrm{u}}\text{→ 4pσ g}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}$ of ⁴He₂ are reported and the electronic structure of the triplet states associated with v = 0 of (1σ_g)²(1σ_u) nsσ and ndλ characterized. The energy levels comprising the $\text{(1σ}{}_{\mathrm{<mtext>g</mtext>}}\text{)}{}^2\text{(1σ}{}_{\mathrm{<mtext>u</mtext>}}\text{)ndλ(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{)}$ and the $\text{(1σ}{}_{\mathrm{<mtext>g</mtext>}}\text{)}{}^2\text{(1σ}{}_{\mathrm{<mtext>u</mtext>}}\text{)ndλ(}{}^3\text{Π}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{)}$ manifolds exhibit strong channel mixing, while the mixing of the $\text{(1σ}{}_{\mathrm{<mtext>g</mtext>}}\text{)}{}^2\text{(1σ}{}_{\mathrm{<mtext>u</mtext>}}\text{)nsσ}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ with the $\text{nd(}{}^3\text{λ}\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{)}$ channel structure is relatively minor. Models based on multichannel quantum defect theory are used to aid in the spectral assignments and to correlate the observed level structures. We show that three-limit and two-limit models adequately represent the bulk of the observed $\text{ndλ(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{)}$ and $\text{ndλ(}{}^3\text{Π}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{,}{}^3\text{Δ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{)}$ channel structures, respectively.     

Energies and orbital sizes for some Rydberg and valence states of the nitrogen molecule

Accurate SCF computations are reported on the Rydberg states of N₂ of electron configurations $\text{---1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$, $\text{---1π}{}_{\mathrm{u}}{}^3\text{3σ}{}_{\mathrm{u}}$, and ---3σ_g2π_g, also on the valence states of the configuration $\text{---1π}{}_{\mathrm{u}}{}^3\text{1π}{}_{\mathrm{g}}$. The Rydberg state calculations supplement those of Lefebvre-Brion and Moser. A comparison is made between the $\text{---1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$ states and the parallel set of states of the $\text{1π}{}_{\mathrm{u}}{}^3\text{1π}{}_{\mathrm{g}}$ configuration. This comparison shows a sharp difference in the ¹Σ⁺ states of the two configurations, the ¹Σ⁺ state being very high in the latter but relatively low in the former configuration. Recknagel coefficients are given for the several states of the two configurations; as expected, these are much smaller for the $\text{1π}{}_{\mathrm{u}}{}^3\text{2π}{}_{\mathrm{u}}$ configuration. Also, the ¹Δ state is relatively lower for the latter configuration.     

Analysis of the B′3Σu− → B3Πg (0,0) emission band of molecular nitrogen

The (0,0) band of the $\text{B′}\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{→ B}{}^3\text{Π}{}_{\mathrm{g}}$ emission (Infrared Afterglow) system of molecular nitrogen has been recorded with a resolution of 0.046 cm^?1 and a line position accuracy of 0.007 cm^?1. Six hundred and seventy-two lines are tabulated into a line list for the 1.53 μm (low-resolution) emission feature. Of these, 482 are assigned as members of the 27 branches of the B′ → B transition, while 150 are identified with the 1PG (3,6) band. Molecular constants for the v = 0 levels of the $\text{B′}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{?}}$ and B³Π_g states have been computed and tabulated.     

Electronic spectra and vibronic coupling of pyrazine

The absorption and fluorescence spectra of pyrazine have been observed in vapor, solution and crystal, and the vibrational structures have been analyzed in detail. The fluorescence spectrum consists of long progressions of the nontotally symmetric vibration ν₅(b_2g), and the absorption spectrum contains also the progression of the corresponding excited state vibration ν′₅(b_2g. However, the pattern of the latter progression is unusual because of the highly anharmonic nature of the potential of the ¹B^3u state, which may be expressed by a functional form containing a quadratic term in the normal coordinate. All the experimental results suggest that the known vibronic interaction between the ${}^1\text{B}{}_{\mathrm{3u}}\text{(n,π}{}^1\text{)}$ state and the ${}^1\text{B}{}_{\mathrm{1u}}\text{(π, π}{}^1\text{)}$ state through the vibration ν₂(b_2g) is strong. The vibronic coupling and the potential of the ¹B_3u state were found to be very sensitive to solvent.     

Infrared spectrum of acetonitrile: Analysis of Coriolis resonance

The Coriolis resonance between ν₄ and ν₇ in CH₃CN and between ν₁ and ν₅, ν₃ and ν₆, and ν₄ and ν₇ in CD₃CN has been analyzed, applying the technique developed by DiLauro and Mills, to obtain the signs of [$\text{ζ}{}_{\mathrm{r,sa}}{}^{\mathrm{y}}\text{(}\text{?p}\text{?Q}{}_{\mathrm{r}}\text{)(}\text{?p}\text{?Q}{}_{\mathrm{sa}}\text{)}$] and the ratio of $\text{?μ}\text{?Q}{}_{\mathrm{r}}$ to $\text{?μ}\text{?Q}{}_{\mathrm{s}}$ for the interacting pairs in CD₃CN. For (ν₄, ν₇) in both CH₃CN and CD₃CN, the sign of [$\text{ζ}{}_{\mathrm{r,sa}}{}^{\mathrm{y}}\text{(}\text{?p}\text{?Q}{}_{\mathrm{r}}\text{)(}\text{?p}\text{?Q}{}_{\mathrm{sa}}\text{)}$] is found to be negative as it is also for (ν₁, ν₅) in CD₃CN. For (ν₃, ν₆) the sign of this interaction term is found to be positive. For a given definition of normal coordinates the signs of these interaction terms give the relative signs of $\text{?p}\text{?Q}{}_{\mathrm{r}}$ and $\text{?p}\text{?Q}{}_{\mathrm{sa}}$; our study also gives approximate values for the corresponding ratio [$\text{(}\text{?p}\text{?Q}{}_{\mathrm{r}}\text{)}\text{(}\text{?p}\text{?Q}{}_{\mathrm{sa}}\text{)}$]     

Reorientational motion of the OH− ion in cubic sodium hydroxide

The rotational motion of the OH^? ion was studied in cubic NaOH at 575 K with quasielastic incoherent neutron scattering. The data are compared to two simple models yielding values for the radius of rotation R, the translational mean square displacement 〈u²〉_H, the rotational jump rate τ^?1 and the rotational diffusion coefficient D_R. The following parameter values are obtained: (a) rotational jump model: $\text{R = 0.95}\text{A}\text{?}$, $\text{〈u}{}^2\text{〉}{}_{\mathrm{H}}\text{= 0.052}\text{A}\text{?}{}^2\text{, τ}{}^{\mathrm{?1}}\text{= 2}\text{meV}$, (b) rotational diffusion model: $\text{R = 0.99}\text{A}\text{?}\text{, 〈u}{}^2\text{〉}{}_{\mathrm{H}}\text{= 0.046}\text{A}\text{?}{}^2\text{, D}{}_{\mathrm{R}}\text{= 0.72}\text{meV}$.     

Assignment of continuous spectra by photofragment spectroscopy: C state of I2

Photofragment spectroscopy has been used to probe the C state of iodine by determining its symmetry and dissociation products. By crossing a molecular beam with a powerful pulsed laser beam in high vacuum and monitoring the arrival times of the recoiling photofragments with a mass spectrometer detector, the translational energy distribution of the photodis-sociation products is measured. From energy balance the fragment internal energy is then calculated. Our peak indicates that the C state dissociates to one excited and one ground state atom. The symmetry of the transition is determined by rotating the plane of polarization of the laser light and measuring a fragment angular distribution. The transition was found to be 1 ← 0. The results are consistent with Mulliken's assignment of the C state as 1441 $\text{1}{}_{\mathrm{u}}\text{(}{}^3\text{Σ}{}^{\mathrm{+}}\text{)}$, but inconsistent with the earlier assignment of 2332 $\text{0}{}_{\mathrm{u}}{}^{\mathrm{?}}\text{(}{}^3\text{Σ}{}^{\mathrm{+}}\text{)}$ by Mathieson and Rees.     

The spectrum and structure of the He2 molecule: Multichannel quantum defect analyses of the triplet levels associated with (1σg)2(1σu)npλ

Emission spectra for the electronic transitions $\text{6–17pπ}{}^3\text{Π}{}_{\mathrm{g}}\text{-2s a}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ and $\text{7–16pσ}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{-2s a}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}$ of He₂ are reported and the electronic structures of $\text{npπ}{}^3\text{Π}{}_{\mathrm{g}}{}^{\mathrm{?}}$ and $\text{np(}{}^2\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{)}$ characterized. The energy levels associated with $\text{(1σ}{}_{\mathrm{g}}\text{)}{}^2\text{(1σ}{}_{\mathrm{u}}\text{)np(}{}^3\text{Σ}{}_{\mathrm{u}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{)}$ exhibit extensive channel mixing, which leads to a breakdown of conventional band models for the higher n¹-members of these Rydberg “series.” However, a model based on multichannel quantum defect theory quantitatively correlates the observed level structures. The higher-energy ($\text{n}{}^1\text{> ～5}$) portions of the $\text{np(}{}^3\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{,}{}^3\text{Π}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{)}$ channels can be represented by two eigen-quantum defects μ₁ = 0.225 and μ₂ = 0.930 and the close- to loose-coupling matrix elements $\text{U}{}_{11}\text{= U}{}_{22}\text{= [N(2N + 1)}{}^{\mathrm{?1}}\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{U}{}_{12}\text{= ?U}{}_{21}\text{= [(N + 1)(2N + 1)}{}^{\mathrm{?1}}\text{]}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$. The inclusion of energy dependence in the μ_α's leads to quantitative correlations for all n¹-values.     

Rotation-vibration analysis of the Coriolis-coupled ν5g, ν6g, ν8g and ν9 bands of H2CCO

Medium resolution infrared grating spectra of gaseous ketene, H₂CCO were recorded between 1000 and 400 cm^?1, both at instrument temperature (40°C) and with cooling (?40°C). Interferometric Fourier spectra were also measured at ?70°C with resolution 0.22 cm^?1 between 450 and 330 cm^?1. The K structure of the fundamentals ν₅, ν₆, ν₈, and ν₉ was assigned. These fundamentals are coupled by a-axis Coriolis interactions. These couplings were analysed on the symmetric top basis for setting up the perturbation matrix and by utilizing the K-dependent Coriolis shifts of levels. A preliminary analysis of the Coriolis intensity anomalies was also undertaken.Band center values from combination differences are $\text{ν}{}_5{}^0\text{= 587.30 (27)}$ and $\text{ν}{}_6{}^0\text{= 528.36 (39)}\text{cm}{}^{\mathrm{?1}}$. Synthetic spectra indicate the band origins of ν₈ and ν₉ to be close to 977.8 and 439.0 cm^?1, respectively. Estimates of Coriolis coupling constants obtained from synthetic spectra are $\text{ζ}{}_{58}{}^{\mathrm{a}}\text{= + 0.33 (5)}$, $\text{ζ}{}_{68}{}^{\mathrm{a}}\text{= + 0.714 (20)}$, $\text{ζ}{}_{59}{}^{\mathrm{a}}\text{= ? 0.774 (20)}$, and $\text{ζ}{}_{69}{}^{\mathrm{a}}\text{= ? 0.30 (2)}$. Approximate ratios of unperturbed vibrational transition moments obtained from spectral simulations are $\text{M}{}_8{}^0\text{:±iM}{}_5{}^0\text{:±iM}{}_6{}^0\text{:M}{}_9{}^0\text{≈ +2:?9:+10:+0.5}$.